Neptunocene

Last updated
Neptunocene
Neptunocene-from-xtal-3D-balls.png
Names
IUPAC name
Bis(η8-cyclooctatetraenyl)neptunium(IV)
Other names
Neptunium cyclooctatetraenide
Np(COT)2
Identifiers
  • 154974-81-9 Yes check.svgY
3D model (JSmol)
  • InChI=1S/2C5H5.Np/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2
    Key: FXDJOXAJBKYPFW-UHFFFAOYSA-N
  • [Np].C1=CC=CC=CC=C1.C1=CC=CC=CC=C1
Properties
C16H16Np
Molar mass 445 g·mol−1
Appearancedark brown crystals as a solid, yellow in dilute solution
insoluble, does not react with water
Solubility in chlorocarbonssparingly soluble (ca. 0.5 g/L)
Hazards
Main hazards radiation hazard, pyrophoric
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Neptunocene, Np(C8H8)2, is an organoneptunium compound composed of a neptunium atom sandwiched between two cyclooctatetraenide (COT2-) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in chlorocarbons, in which it is sparingly soluble. [1] [2] [3] [4] [5] The compound is quite air-sensitive. [1] [2] [5]

Contents

It was one of the first organoneptunium compounds to be synthesised, and is a member of the actinocene family of actinide-based metallocenes. [2]

Structure

The sandwich structure of neptunocene has been determined by single crystal XRD. [4] The COT2- rings are found to be planar with 8 equivalent C–C bonds of 1.385 Å length, and sit parallel in an eclipsed conformation. The Np–COT distance (to the ring centroid) is 1.909 Å and the individual Np–C distances are 2.630 Å. [4]

Neptunocene assumes a monoclinic crystal structure (P21/n space group) which is isomorphous to uranocene and thorocene but not to plutonocene. [4]

Synthesis and properties

Neptunocene was first synthesised in 1970 by reacting neptunium(IV) chloride (NpCl4) with dipotassium cyclooctatetraenide (K2(C8H8)) in diethyl ether or THF: [1]

NpCl4 + 2 K2(C8H8) → Np(C8H8)2 + 4 KCl

The same reaction conditions have been routinely reproduced since then for the synthesis of the compound. [3] [4]

The three actinocenes uranocene, neptunocene, and plutonocene share virtually identical chemistry: they do not react in the presence of water or dilute base, but are very air-sensitive, quickly forming oxides. [1] [2] [3] All three are only slightly soluble (up to about 10−3 M concentrations) in aromatic or chlorinated solvents such as benzene, toluene, carbon tetrachloride or chloroform. [1] [2] [4] [5]

Related Research Articles

Berkelium Chemical element, symbol Bk and atomic number 97

Berkelium is a transuranic radioactive chemical element with the symbol Bk and atomic number 97. It is a member of the actinide and transuranium element series. It is named after the city of Berkeley, California, the location of the Lawrence Berkeley National Laboratory where it was discovered in December 1949. Berkelium was the fifth transuranium element discovered after neptunium, plutonium, curium and americium.

Metallocene

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride, vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

Neptunium Chemical element, symbol Np and atomic number 93

Neptunium is a chemical element with the symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after the planet Uranus, led to it being named after Neptune, the next planet beyond Uranus. A neptunium atom has 93 protons and 93 electrons, of which seven are valence electrons. Neptunium metal is silvery and tarnishes when exposed to air. The element occurs in three allotropic forms and it normally exhibits five oxidation states, ranging from +3 to +7. It is radioactive, poisonous, pyrophoric, and capable of accumulating in bones, which makes the handling of neptunium dangerous.

Cyclooctatetraene Chemical compound

1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as [8]annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of its stoichiometric relationship to benzene, COT has been the subject of much research and some controversy.

Uranocene, U(C8H8)2, is an organouranium compound composed of a uranium atom sandwiched between two cyclooctatetraenide rings. It was one of the first organoactinide compounds to be synthesized. It is a green air-sensitive solid that dissolves in organic solvents. Uranocene, a member of the "actinocenes," a group of metallocenes incorporating elements from the actinide series. It is the most studied bis[8]annulene-metal system, although it has no known practical applications.

Sandwich compound

In organometallic chemistry, a sandwich compound is a chemical compound featuring a metal bound by haptic covalent bonds to two arene ligands. The arenes have the formula CnHn, substituted derivatives (for example Cn(CH3)n) and heterocyclic derivatives (for example BCnHn+1). Because the metal is usually situated between the two rings, it is said to be "sandwiched". A special class of sandwich complexes are the metallocenes.

Organoactinide chemistry

Organoactinide chemistry is the science exploring the properties, structure and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond.

Organouranium chemistry

Organouranium chemistry is the science exploring the properties, structure and reactivity of organouranium compounds, which are organometallic compounds containing a carbon to uranium chemical bond. The field is of some importance to the nuclear industry and of theoretical interest in organometallic chemistry.

Ken Raymond American inorganic chemist

Kenneth Norman Raymond is a bioinorganic and coordination chemist. He is Chancellor's Professor of Chemistry at University of California, Berkeley, Professor of the Graduate School, the Director of the Seaborg Center in the Chemical Sciences Division at Lawrence Berkeley National Laboratory, and the President and Chairman of Lumiphore.

Rhodocene chemical compound

Rhodocene is a chemical compound with the formula [Rh(C5H5)2]. Each molecule contains an atom of rhodium bound between two planar aromatic systems of five carbon atoms known as cyclopentadienyl rings in a sandwich arrangement. It is an organometallic compound as it has (haptic) covalent rhodium–carbon bonds. The [Rh(C5H5)2] radical is found above 150 °C or when trapped by cooling to liquid nitrogen temperatures (−196 °C). At room temperature, pairs of these radicals join via their cyclopentadienyl rings to form a dimer, a yellow solid.

Ligand bond number

Ligand bond number (LBN) represents the effective total number of ligands surrounding a metal center, M. More simply, it represents the number of coordination sites occupied on the metal. Based on the covalent bond classification method, the equation for the LBN is as follows:

Neptunium(VI) fluoride Chemical compound

Neptunium(VI) fluoride (NpF6) is the highest fluoride of neptunium, it is also one of seventeen known binary hexafluorides. It is an orange volatile crystalline solid. It is relatively hard to handle, being very corrosive, volatile and radioactive. Neptunium hexafluoride is stable in dry air but reacts vigorously with water.

Actinocene

Actinocenes are a family of organoactinide compounds consisting of metallocenes containing elements from the actinide series. They typically have a sandwich structure with two dianionic cyclooctatetraenyl ligands (COT2-, which is C
8
H2−
8
) bound to an actinide-metal center (An) in the oxidation state IV, resulting in the general formula An(C8H8)2.

Thorium compounds

Many compounds of thorium are known: this is because thorium and uranium are the most stable and accessible actinides and are the only actinides that can be studied safely and legally in bulk in a normal laboratory. As such, they have the best-known chemistry of the actinides, along with that of plutonium, as the self-heating and radiation from them is not enough to cause radiolysis of chemical bonds as it is for the other actinides. While the later actinides from americium onwards are predominantly trivalent and behave more similarly to the corresponding lanthanides, as one would expect from periodic trends, the early actinides up to plutonium have relativistically destabilised and hence delocalised 5f and 6d electrons that participate in chemistry in a similar way to the early transition metals of group 3 through 8: thus, all their valence electrons can participate in chemical reactions, although this is not common for neptunium and plutonium.

Plutonocene Chemical compound

Plutonocene, Pu(C8H8)2, is an organoplutonium compound composed of a plutonium atom sandwiched between two cyclooctatetraenide (COT2-) rings. It is a dark red, very air-sensitive solid that is sparingly soluble in toluene and chlorocarbons. Plutonocene is a member of the actinocene family of metallocenes incorporating actinide elements in the +4 oxidation state.

Neptunium(III) fluoride or neptunium trifluoride is a salt of neptunium and fluorine with the formula NpF3.

Neptunium(IV) fluoride Chemical compound

Neptunium(IV) fluoride or neptunium tetrafluoride is a inorganic compound with the formula NpF4. It is a green salt and is isostructural with UF4.

Neptunium(V) fluoride or neptunium pentafluoride is a chemical compound of neptunium and fluorine with the formula NpF5.

Organoneptunium chemistry is the chemical science exploring the properties, structure and reactivity of organoneptunium compounds, which are organometallic compounds containing a carbon to neptunium chemical bond. Several such compounds exist even though the element itself, neptunium, is man-made and highly radioactive: tricyclopentadienylneptunium-chloride, tetrakis(cyclopentadienyl)neptunium(IV) and neptunocene Np(C8H8)2.

Magnesocene, also known as bis(cyclopentadienyl)magnesium(II) and sometimes abbreviated as MgCp2, is an organometallic compound with the formula Mg(η5-C5H5)2. It is an example of an s-block main group sandwich compound, structurally related to the d-block element metallocenes, and consists of a central magnesium atom sandwiched between two cyclopentadienyl rings.

References

  1. 1 2 3 4 5 Karraker, David G.; Stone, John Austin.; Jones, Erwin Rudolph.; Edelstein, Norman. (1970). "Bis(cyclooctatetraenyl)neptunium(IV) and bis(cyclooctatetraenyl)plutonium(IV)". Journal of the American Chemical Society. 92 (16): 4841–4845. doi:10.1021/ja00719a014. ISSN   0002-7863.
  2. 1 2 3 4 5 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 1278–1280. ISBN   9780750633659.
  3. 1 2 3 Eisenberg, David C.; Streitwieser, Andrew; Kot, Wing K. (1990). "Electron transfer in organouranium and transuranium systems". Inorganic Chemistry. 29 (1): 10–14. doi:10.1021/ic00326a004. ISSN   0020-1669.
  4. 1 2 3 4 5 6 Ridder, D. J. A. De; Rebizant, J.; Apostolidis, C.; Kanellakopulos, B.; Dornberger, E. (1996). "Bis(cyclooctatetraenyl)neptunium(IV)". Acta Crystallographica Section C. 52 (3): 597–600. doi:10.1107/S0108270195013047. ISSN   1600-5759.
  5. 1 2 3 Yoshida, Zenko; Johnson, Stephen G.; Kimura, Takaumi; Krsul, John R. (2006). "Neptunium". In Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean (eds.). The Chemistry of the Actinide and Transactinide Elements (PDF). 3 (3rd ed.). Dordrecht, the Netherlands: Springer. pp. 699–812. doi:10.1007/1-4020-3598-5_6.